Use of modified polyaspartic acids in washing agents

ABSTRACT

The use of modified polyaspartic acids which are obtainable by polycondensation of aspartic acid in the presence of, in each case based on the aspartic acid employed, 
     (a) 2.5 to 25 mol % of amines with at least 6 carbon atoms 
     (b) at least 2% by weight of phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acids, phosphorus pentoxide, phosphonic acids or mixtures of said acids, 
     at temperatures of at least 120° C. and subsequent hydrolysis with bases to give modified polyaspartic acids with a phosphorus content of from 0.5 to 10% by weight, as additive to detergents, and detergents which contain the modified polyaspartic acids in amounts of from 0.1 to 20% by weight.

The invention relates to the use of modified polyaspartic acids indetergents and to detergents which contain the modified polyasparticacids in amounts of from 0.1 to 20% by weight.

EP-A-0 454 126 discloses detergents which contain 10 to 40% by weight ofa surfactant, 5 to 50% by weight of at least one sodium aluminumsilicate, 0.5 to 70% by weight of at least one conventionally usedadditive and 5 to 50% by weight of at least one polyamino acid,preferably polyaspartic acid or polyglutamic acid, as organic cobuilder.Hompolymers of aspartic acid as ingredient of modern detergentformulations are disclosed, for example, in WO-A 94/14939 and WO-A94/10282. Polyaspartic acid improves the soil release capacity ofgranular detergents.

WO-A 95/16020 discloses the use of polyaspartic acid which has beenprepared by polycondensation of aspartic acid in the presence ofphosphoric acid in a molar ratio of from 1:0.05 to 1:10 at temperaturesof at least 120° C. to give polysuccinimide and subsequent hydrolysis ofthe polysuccinimide with bases to give at least partially neutralizedpolyaspartic acid, as additive to detergents and cleaners in amounts offrom 0.1 to 10% by weight. The polyaspartic acids prepared in this wayhave the advantage, compared with polyaspartic acids which can beprepared by other processes, that they have considerably betterbiodegradability.

WO-A 94/01486 discloses modified polyaspartic acids obtainable bypolycondensation of aspartic acids with fatty acids, polybasiccarboxylic acids, anhydrides of polybasic carboxylic acids, polybasichydroxy carboxylic acids, monobasic polyhydroxy carboxylic acids,alcohols, amines, alkoxylated alcohols and alkoxylated amines,aminosaccharides, carbohydrates, sugar carboxylic acids and/ornon-proteinogenous amino carboxylic acids. The modified polyasparticacids are used as additive to reduced-phosphate and phosphate-freedetergents and cleaners, as water-treatment agent and as scale inhibitorin the evaporation of sugar juice.

Although the polyaspartic acids described above confer dispersantproperties on the detergent formulations, they do not, on use of thesame amount, achieve the same encrustation-inhibiting effect ofcommercial polymeric cobuilders such as copolymers of acrylic acid andmaleic acid with an average molecular weight of 70,000 or of polymaleicacids with a molecular weight of from 1000 to 3000.

It is an object of the present invention to provide an organic cobuilderbased on polyaspartic acid which is an improvement compared with theprior art.

We have found that this object is achieved by using modifiedpolyaspartic acids obtainable by polycondensation of aspartic acid inthe presence of, in each case based on the aspartic acid employed,

(a) 2.5 to 25 mol % of amines with at least 6 carbon atoms and

(b) at least 5% by weight of phosphoric acid, phosphorous acid,hypophosphorous acid, polyphosphoric acids, phosphorus pentoxide,phosphonic acids or mixtures of said acids,

at temperatures of at least 120° C. and subsequent hydrolysis with basesto give modified polyaspartic acids with a phosphorus content of from0.5 to 10% by weight, as additive to detergents.

The invention additionally relates to detergents which comprise at leastone surfactant and an organic cobuilder and, where appropriate, otherconventional ingredients, where the detergents comprise as organiccobuilder 0.1 to 20% by weight of a modified polyaspartic acidobtainable by polycondensation of aspartic acid in the presence of, ineach case based on the aspartic acid employed,

(a) 2.5 to 25 mol % of amines with at least 6 carbon atoms and

(b) at least 2% by weight of phosphoric acid, phosphorous acid,hypophosphorous acid, polyphosphoric acids, phosphorus pentoxide,phosphonic acids or mixtures of said acids,

at temperatures of at least 120° C. and subsequent hydrolysis with basesto give modified polyaspartic acids with a phosphorus content of from0.5 to 10% by weight.

The modified polyaspartic acids to be employed according to theinvention as organic cobuilder in detergents can be prepared, forexample, by polycondensation of D- or DL-aspartic acid with thecompounds indicated above under (a) and (b). Suitable compounds ofcomponent (a) are amines with at least 6 carbon atoms. These amines arepreferably primary and/or secondary C₈ -C₂₂ -alkylamines. Preferredsecondary alkylamines are those compounds in which at least one alkylradical has at least 6 carbon atoms, while the other alkyl radical canhave any number of carbon atoms, eg. C₁ -C₅ -alkyl. If tertiary aminesare employed, they preferably contain an alkyl radical with at least 6carbon atoms, preferably with at least 10 carbon atoms, while the twoother alkyl substituents are preferably C₁ -C₅ -alkyl groups.

Examples of amines suitable as component (a) are 2-ethylhexylamine,hexylamine, octylamine, decylamine, tridecylamine, cetylamine,stearylamine, palmitylamine, oleylamine, tallow fatty amine, coconutfatty amine, hydrogenated tallow fatty amine, aniline, toluidine orother substituted aromatic amines and polyisobutenamines which have, forexample, 5 to 30 isobutene units. Amines which are particularlypreferably employed are dodecylamine, tridecylamine, octadecylamine,stearylamine, palmitylamine, oleylamine, tallow fatty amine or mixturesof these amines. Based on 1 mol of the aspartic acid employed in thepolycondensation, from 2.5 to 25, preferably 2.5 to 15, mol % of atleast one amine are used.

The polycondensation of the aspartic acid takes place in the presence ofphosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoricacids, phosphorus pentoxide, phosphonic acids or mixtures thereof.Preferably employed as phosphoric acid is technical, 75-85% strengthaqueous orthophosphoric acid. However, it is also possible to use 100%strength orthophosphoric acid or metaphosphoric acid. Polyphosphoricacids can likewise be employed, eg. diphosphoric acid (pyrophosphoricacid), triphosphoric acid and higher phosphoric acid homologs. If morethan the stoichiometric amounts of phosphoric acid are employed in thecondensation, the polycondensation reaction is carried out in phosphoricacid as solvent and diluent. Also suitable as compounds of component (b)are phosphorus pentoxide and phosphonic acids. The phosphonic acids canbe characterized, for example, by means of the formula ##STR1## where Ris phenyl or C₁ -C₂₂ -alkyl. The compounds of component (b) can beemployed either alone or in a mixture in the preparation of the modifiedpolyaspartic acids. They are used in the cocondensation in an amount ofat least 5% of the weight of aspartic acid employed. The ratio ofaspartic acid to phosphoric acid by weight is, for example, 1:0.05 to1:10, preferably 1:0.4. Preferably used to prepare the modifiedpolyaspartic acids are

(a) primary and/or secondary C₈ -C₂₂ -alkylamines and

(b) phosphoric acid, phosphorous acid, polyphosphoric acid or mixturesthereof.

The modified polyaspartic acids to be used according to the inventionare particularly preferably prepared by polycondensation of

(a) dodecylamine, tridecylamine, stearylamine, palmitylamine,oleylamine, tallow fatty amine, coconut fatty amine, hydrogenated tallowfatty amine or mixtures of these amines and

(b) phosphoric acid and/or phosphorous acid.

The condensations are carried out at temperatures of at least 120° C.,usually in the range from 150 to 250, preferably 160 to 220° C. Based onthe aspartic acid employed, 2.5 to 25 mol % of at least one compound ofcomponent (a) are used. The polycondensation can be carried out, forexample, in such a way that aqueous solutions of components (a) and (b)are added successively or simultaneously to finely divided asparticacid. The sequence of the addition of the aqueous solutions ofcomponents (a) and (b) is immaterial. The components (a) and (b) can bebrought into contact with the aspartic acid at room temperature, eg. at20° C., or else at a higher temperature, eg. at 150° C., undercondensation conditions. If components (a) and (b) are mixed in the formof an aqueous solution with the aspartic acid, initially water isdistilled out of the reaction mixture. The polycondensation then takesplace. However, the polycocondensation can also be carried out in theabsence of water. Components (a) and (b) can also be combined andcondensed with aspartic acid in the absence of water. Thepolycocondensation can also be carried out in such a way that initiallycomponents (a) and (b) are reacted together at room temperature orelevated temperature, eg. from 20 to 250° C., and the productsobtainable in this reaction are cocondensed with aspartic acid. Thestructure of the reaction products has not yet been elucidated. They arepresumably salts and/or products which can be characterized by means ofthe following formulae: ##STR2##

In the formulae indicated above, at least one substituent

R¹,R² or R³ is an alkyl group with at least 6 carbon atoms, preferablyC₈ -C₂₂ -alkyl, and the others are then H or C₁ -C₂₂ -, preferably C₁-C₅ -alkyl,

R⁴ is phenyl or C₁ -C₂₂ -alkyl.

The reaction products indicated above contain components (a) and (b) inthe molar ratio 1:1. However, it is possible to use less than 1 mol ofcomponent (a) or the equivalent amount of compounds of component (a),based on the compounds of component (b), eg. up to 3 mol of amine can beused per mol of phosphoric acid, and up to 2 mol of amine can be usedper mol of phosphorous acid.

The polycondensation of aspartic acid with components (a) and (b)initially results in products which have succinimide units. The productscan be washed with water to remove compounds of component (b), eg.uncondensed phosphoric acid. The polymers containing succinimide unitsare converted into polymers containing aspartic acid units by hydrolysiswith bases. Bases which are preferably used are sodium or potassiumhydroxide solution, but ammonia or amines such as ethanolamine,diethanolamine or triethanolamine can also be used for this purpose.

The washing out of the phosphoric acid or the other acids mentionedunder (b) with water results in products which still contain boundphosphorus. The content of phosphorus in the modified aspartic acids is0.5 to 10, preferably 0.6 to 6, % by weight. Modified polyaspartic acidswhich are particularly preferred for the use according to the inventionare those whose phosphorus content is 0.6 to 2% by weight.

The modified polyaspartic acids are employed in an amount of from 0.1 to20, preferably 1 to 15, % by weight in detergent formulations.

The detergents can be in powder form or else in a liquid formulation.The composition of the detergents and cleaners may vary widely.Detergent and cleaner formulations normally contain 2 to 50% by weightof surfactants and, where appropriate, builders. These data apply bothto liquid and to powder detergents. Detergent and cleaner formulationscustomary in Europe, the USA and Japan are tabulated, for example, inChemical and Engn. News, 67 (1989) 35. Further details of thecomposition of detergents and cleaners are to be found in Ullmann'sEnzyklopadie der technischen Chemie, Verlag Chemie, Weinheim 1983, 4thEdition, pages 63 to 160.

Reduced-phosphate detergents mean formulations which contain not morethan 25% by weight of phosphate, calculated as pentasodium triphosphate.The detergents can be heavy duty detergents or speciality detergents.Suitable surfactants are both anionic and nonionic, or mixtures ofanionic and nonionic, surfactants. The preferred surfactant content ofthe detergents is 8 to 30% by weight.

Examples of suitable anionic surfactants are fatty alcohol sulfates offatty alcohols with 8 to 22, preferably 10 to 18, carbon atoms, eg. C₉-C₁₁ -alcohol sulfates, C₁₂ -C₁₃ -alcohol sulfates, cetyl sulfate,myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fattyalcohol sulfate.

Other suitable anionic surfactants are sulfated, ethoxylated C₈ -C₂₂-alcohols and their soluble salts. Compounds of this type are prepared,for example, by initially alkoxylating a C₈ -C₂₂ -, preferably C₁₀ -C₁₈-alcohol, and subsequently sulfating the alkoxylation product. Ethyleneoxide is preferably used for the alkoxylation, in which case 2 to 50,preferably 3 to 20, mol of ethylene oxide are employed per mol of fattyalcohol. However, the alcohols can also be alkoxylated with propyleneoxide alone and, where appropriate, butylene oxide. Also suitable arethose alkoxylated C₈ -C₂₂ -alcohols which contain ethylene oxide andpropylene oxide or ethylene oxide and butylene oxide. The alkoxylated C₈-C₂₂ -alcohols may contain the ethylene oxide, propylene oxide andbutylene oxide units in the form of blocks or in random distribution.

Further suitable anionic surfactants are alkylsulfonates such as C₈ -C₂₄-, preferably C₁₀ -C₁₈ -alkanesulfonates, as well as soaps such as thesalts of C₈ -C₂₄ -carboxylic acids.

Further suitable anionic surfactants are linear C₉ -C₂₀-alkylbenzenesulfonates (LAS). The polymers according to the inventionare preferably employed in detergent formulations with less than 4% ofLAS, particularly preferably in LAS-free formulations.

The anionic surfactants are preferably added to the detergent in theform of salts. Suitable cations in these salts are alkali metal ionssuch as sodium, potassium and lithium ions, and ammonium ions such ashydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium ions.

Examples of suitable nonionic surfactants are alkoxylated C₈ -C₂₂-alcohols. The alkoxylation can be carried out with ethylene oxide,propylene oxide and/or butylene oxide. It is possible to employ assurfactant in this connection all alkoxylated alcohols which contain atleast two molecules of one of the abovementioned alkylene oxides in theadduct. Also suitable in this connection are block copolymers ofethylene oxide, propylene oxide and/or butylene oxide, or adducts whichcontain said alkylene oxides in random distribution. From 2 to 5,preferably 3 to 20, mol of at least one alkylene oxide are used per molof alcohol. Ethylene oxide is preferably used as alkylene oxide. Thealcohols preferably have 10 to 18 carbon atoms.

Another class of nonionic surfactants comprises alkyl polyglucosideswith 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain.These compounds contain 1 to 20, preferably 1.1 to 5, glucoside units.

Another class of nonionic surfactants comprises N-alkylglucamides of thegeneral structure III or IV ##STR3## where A is C₆ -C₂₂ -alkyl, B is Hor C₁ -C₄ -alkyl and C is polyhydroxyalkyl with 5 to 12 carbon atoms andat least 3 hydroxyl groups. A is preferably C₁₀ -C₁₈ -alkyl, B ispreferably CH₃ and C is preferably a C₅ or C₆ radical. Compounds of thistype are obtained, for example, by acylation of reductively aminatedsugars with acid chlorides of C₁₀ -C₁₈ -carboxylic acids. The nonionicsurfactants preferably present in the detergent formulations are C₁₀-C₁₆ -alcohols preferably ethoxylated with 3-12 mol of ethylene oxide,and particularly preferably ethoxylated fatty alcohols.

Further suitable and preferred surfactants are the endgroup-capped fattyamide alkoxylates of the general formula

    R.sup.1 --CO--NH--(CH.sub.2).sub.n --O--(AO).sub.x --R.sup.2

where

R¹ is C₅ -C₂₁ -alkyl or -alkenyl,

R² is C₁ -C₄ -alkyl,

A is C₂ -C₄ -alkylene,

n is 2 or 3, and

x is from 1 to 6,

which are disclosed in WO-A 95/11225.

Examples of such compounds are the products of the reaction ofN-butyltriglycolamine of the formula H₂ N--(CH₂ --CH₂ --O)₃ --C₄ H₉ withmethyl dodecanoate or the products of the reaction ofethyltetraglycolamine of the formula H₂ N--(CH₂ --CH₂ --O)₄ --C₂ H₅ witha commercial mixture of saturated C₈ -C₁₈ -fatty acid methyl esters.

The powdered or granular detergents and, where appropriate, alsostructured liquid detergents additionally contain one or more inorganicbuilders. Suitable substances are all conventional inorganic builderssuch as alumosilicates, silicates, carbonates and phosphates.

Examples of suitable inorganic builders are alumosilicates withion-exchanging properties such as zeolites. Various types of zeolitesare suitable, especially zeolites A, X, B, P, MAP and HS in their Naform or in forms in which Na is partly replaced by other cations such asLi, K, Ca, Mg or ammonium. Suitable zeolites are described, for example,in EP-A 0 038 591, EP-A 0 021 491, EP-A 0 087 035, U.S. Pat. No.4,604,224, GB-A 2 013 259, EP-A 0 522 726, EP-A 0 384 070A and WO-A94/24251.

Other suitable inorganic builders are, for example, amorpous orcrystalline silicates such as amorphous disilicates, crystallinedisilicates such as the sheet silicate SKS-6 (manufactured by HoechstAG). The silicates can be employed in the form of their alkali metal,alkaline earth metal or ammonium salts. Na, Li and Mg silicates arepreferably employed.

Further suitable inorganic builders are carbonates and bicarbonates.These can be employed in the form of their alkali metal, alkaline earthmetal or ammonium salts. Preferably employed are Na, Li and Mgcarbonates or bicarbonates, especially sodium carbonate and/or sodiumbicarbonate.

The inorganic builders can be present in the detergents in amounts offrom 0 to 60% by weight, together with organic cobuilders to be usedwhere appropriate. The inorganic builders can be incorporated eitheralone or in any combination with one another into the detergent. Theyare added to powdered or granular detergents in amounts of from 10 to60% by weight, preferably from 20 to 50% by weight. Inorganic buildersare added in amounts of up to 40% by weight, preferably up to 20% byweight, to structured (multiphase) liquid detergents. They are suspendedin the liquid formulation ingredients.

Powdered or granular, and liquid detergent formulations contain organiccobuilders in amounts of from 0.1 to 20% by weight, preferably from 1 to15% by weight, together with inorganic builders. The powdered orgranular heavy duty detergents may additionally contain as otherconventional ingredients a bleaching system consisting of at least onebleach, where appropriate in combination with a bleach activator and/ora bleach catalyst.

Suitable bleaches are perborates and percarbonates in the form of theiralkali metal, in particular their Na, salts. They are present in theformulations in amounts of from 5 to 30% by weight, preferably 10 to 25%by weight. Further suitable bleaches are inorganic and organic peracidsin the form of their alkali metal or magnesium salts or partly also inthe form of the free acids. Examples of suitable organic percarboxylicacids or salts thereof are Mg monoperphthalate, phthalimidopercaproicacid and diperdodecanedioic acid. An example of an inorganic peracidsalt is potassium peroxomonosulfate (Oxone).

Examples of suitable bleach activators are

acylamines such as tetraacetylethylenediamine, tetraacetylglycoluril,N,N'-diacetyl-N,N'-dimethylurea and1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine

acylated lactams such as acetylcaprolactam, octanoylcaprolactam andbenzoylcaprolactam

substituted phenol esters of carboxylic acids such as Naacetoxybenzenesulfonate, Na octanoyloxybenzenesulfonate and Nanonanoyloxybenzenesulfonate

acylated sugars such as pentaacetylglucose

anthranil derivatives such as 2-methylanthranil or 2-phenylanthranil

enol esters such as isopropenyl acetate

oxime esters such as acetone O-acetyloxime

carboxylic anhydrides such as phthalic anhydride or acetic anhydride.

Tetraacetylethylenediamine and Na nonanoyloxybenzenesulfonates arepreferably employed as bleach activators. The bleach activators areadded to heavy duty detergents in amounts of from 0.1 to 15% by weight,preferably from 1.0 to 8.0% by weight, particularly preferably from 1.5to 6.0% by weight.

Suitable bleach catalysts are quaternized imines and sulfone imines asdescribed in U.S. Pat. No. 5,360,568, U.S. Pat. No. 5,360,569 and EP-A 0453 003, and Mn complexes, cf., for example, WO-A 94/21777. If bleachcatalysts are employed in the detergent formulations, they are presentin amounts of up to 1.5% by weight, preferably up to 0.5% by weight, andin the case of the very active manganese complexes in amounts of up to0.1% by weight.

The detergents preferably contain an enzyme system. This comprisesproteases, lipases, amylases and cellulases normally employed indetergents. The enzyme system may be confined to single enzymes orcomprise a combination of various enzymes. The commercial enzymes areadded to the detergents as a rule in amounts of from 0.1 to 1.5% byweight, preferably 0.2 to 1.0% by weight, of the formulated enzyme.Examples of suitable proteases are Savinase and Esperase (manufacturedby Novo Nordisk). An example of a suitable lipase is Lipolase(manufactured by Novo Nordisk). An example of a suitable cellulase isCelluzym (manufactured by Novo Nordisk).

The detergents contain, as other conventional ingredients, preferablysoil release polymers and/or antiredeposition agents. Examples of theseare

polyesters of polyethylene oxides with ethylene glycol and/or propyleneglycol and aromatic dicarboxylic acids or aromatic and aliphaticdicarboxylic acids. Polyesters of polyethylene oxides, which areendgroup-capped at one end, with dihydric and/or polyhydric alcohols anddicarboxylic acids. Polyesters of these types are disclosed, forexample, in U.S. Pat. No. 3,557,039, GB-A 1 154 730, EP-A 0 185 427,EP-A 0 241 984, EP-A 0 241 985, EP-A 0 272 033 and U.S. Pat. No.5,142,020.

Further suitable soil release polymers are amphiphilic graft copolymersof vinyl and/or acrylic esters on polyalkylene oxides, cf. U.S. Pat. No.4,746,456, U.S. Pat. No. 4,846,995, DE-A 3 711 299, U.S. Pat. No.4,904,408, U.S. Pat. No. 4,846,994 and U.S. Pat. No. 4,849,126 ormodified celluloses such as methylcellulose, hydroxypropylcellulose orcarboxymethylcellulose.

The detergent formulations contain 0 to 2.5% by weight, preferably 0.2to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight, ofantiredeposition agents and soil release polymers. Soil release polymerswhich are preferably employed are the graft copolymers of vinyl acetateon polyethylene oxide of molecular weight 2500-8000 in the ratio 1.2:1to 3.0:1 by weight, which are disclosed in U.S. Pat. No. 4,746,456, andcommercial polyethylene terephthalate/polyoxyethylene terephthalates ofmolecular weight 3000 to 25,000 from polyethylene oxides of molecularweight 750 to 5000 with terephthalic acid and ethylene oxide and a molarratio of polyethylene terephthalate to polyoxyethylene terephthalate offrom 8:1 to 1:1, and the block polycondensates which are disclosed inDE-A 4 403 866 and which contain blocks of (a) ester units frompolyalkylene glycols with a molecular weight of 500 to 7500 andaliphatic dicarboxylic acids and/or monohydroxy monocarboxylic acids and(b) ester units from aromatic dicarboxylic acids and polyhydricalcohols. These amphiphilic block copolymers have molecular weights offrom 1500 to 25,000.

A typical powder or granular heavy duty detergent can have the followingcomposition, for example:

3-50, preferably 8-30, % by weight of at least one anionic and/ornonionic surfactant,

5-50, preferably 15-42.5, % by weight of at least one inorganic builder,

5-30, preferably 10-25, % by weight of an inorganic bleach,

0.1-15, preferably 1-8, % by weight of a bleach activator,

0-1, preferably up to a maximum of 0.5, % by weight of a bleachcatalyst,

0.05-5% by weight, preferably 0.2-2.5% by weight, of a color transferinhibitor based on water-soluble homopolymers of N-vinylpyrrolidone orN-vinylimidazole, water-soluble copolymers of N-vinylimidazole andN-vinylpyrrolidone, cross-linked copolymers of N-vinylimidazole andN-vinylpyrrolidone with a particle size of from 0.1 to 500, preferablyup to 250 μm, these copolymers containing 0.01-5, preferably 0.1-2, % byweight of N,N'-divinylethyleneurea as cross-linker. Further colortransfer inhibitors are water-soluble and crosslinked polymers of4-vinylpyridine N-oxide which are obtainable by polymerizing4-vinylpyridine and subsequently oxidizing the polymers.

0.1-20, preferably 1-15, % by weight of at least one modifiedpolyaspartic acid to be used according to the invention as organiccobuilder,

0.2-1.0% by weight of protease,

0.2-1.0% by weight of lipase,

0.3-1.5% by weight of a soil release polymer.

A bleach system is often entirely or partly dispensed with incolor-sparing speciality detergents (for example in color detergents). Atypical color detergent in powder or granule form can have, for example,the following composition:

3-50, preferably 8-30, % by weight of at least one anionic and/ornonionic surfactant,

10-60, preferably 20-55, % by weight of at least one inorganic builder,

0-15, preferably 0-5, % by weight of an inorganic bleach,

0.05-5% by weight, preferably 0.2-2.5% by weight, of a color transferinhibitor, see above,

0.1-20, preferably 1-15, % by weight of at least one modifiedpolyaspartic acid described above as organic cobuilder,

0.2-1.0% by weight of protease,

0.2-1.0% by weight of cellulase,

0.2-1.5% by weight of a soil release polymer, eg. a graft copolymer ofvinyl acetate on polyethylene glycol.

The detergents in powder or granule form can contain as otherconventional ingredients up to 60% by weight of inorganic fillers.Sodium sulfate is normally used for this purpose. However, thedetergents according to the invention preferably have a low fillercontent and contain up to 20% by weight, particularly preferably up to8% by weight, of fillers.

The detergents according to the invention may have various apparentdensities in the range from 300 to 950 g/l. Modern compact detergentshave, as a rule, high apparent densities, eg. 550-950 g/l, and agranular structure.

The liquid detergents according to the invention contain, for example,

5-60, preferably 10-40, % by weight of at least one anionic and/ornonionic surfactant,

0.05-5% by weight, preferably 0.2-2.5% by weight, of a color transferinhibitor (see above),

0.1-20, preferably 1-15, % by weight of at least one modifiedpolyaspartic acid described above, as cobuilder,

0-1.0% by weight of protease,

0-1.0% by weight of cellulase,

0-1.5% by weight of a soil release polymer and/or antiredepositionagent,

0-60% by weight of water,

0-10% by weight of alcohols, glycols, such as ethylene glycol,diethylene glycol, propylene glycol or glycerol.

The detergents may, where appropriate, contain further conventionaladditives. Examples of other additives which may be present whereappropriate are complexing agents, phosphonates, optical brighteners,dyes, perfume oils, foam suppressants and corrosion inhibitors.

The percentages in the examples are % by weight unless otherwiseindicated.

EXAMPLES Preparation of Cobuilders 1 to 3

A mixture of 133 g of L-aspartic acid, 326 g of 75% strength phosphoricacid and the amounts of amine stated in Table 1 is introduced into areactor which has a capacity of 2 l and is equipped with a stirrer anddistillation set and is heated with stirring to 100° C. Water is removedfrom the mixture under water-pump vacuum and at 100° C. The mixture isthen heated to 180° C. and maintained at this temperature for 3 hours tocarry out the polycondensation. The contents of the reactor are thencooled, the polycondensate is taken up in 1 1 of water, the mixture isfiltered and the insoluble residue is washed with 1 l of water. Thepolycondensate which has been washed with water is suspended in 500 mlof water, heated to 60° C. and hydrolyzed by adding 25% strength aqueoussodium hydroxide solution at such a rate that the pH of the reactionsolution is always from 8 to 10. The hydrolysis is complete wheninsolubles are no longer present. Clear or cloudy aqueous solutions ofpolycocondensates result. A sample of the aqueous solution of thepolycondensate is dried and analyzed for the phosphorus content. Table 1contains information on the properties of the reaction productsobtained.

Preparation of Cobuilder 4

150 g of water and 20.4 g of sulfuric acid are introduced into thereactor described above, and then 39.8 g of tridecylamine andsubsequently 133 g of aspartic acid are added. The reaction mixture isheated with stirring to 100° C. and water is removed by distillationunder waterpump vacuum. The polycondensation takes place by heating themixture at 180° C. for 5 hours. After cooling, the contents of thereactor are suspended in 70 g of water. 130 g 40 of 25% strength aqueoussodium hydroxide solution are mixed into this suspension over the courseof 15 minutes. The pH of the solution is 7.

                  TABLE 1                                                         ______________________________________                                                                          P     Mole-                                                            Solids content                                                                             cular                                                            content                                                                              of the                                                                              weight                                                           of the cocon-                                                                              of the                                Co-   Amine                solution                                                                             densate                                                                             cocon-                                builder                                                                             [g]          Acid    [%]    [%]   densate                               ______________________________________                                        1     20.0 Tridecylamine                                                                         H.sub.3 PO.sub.4                                                                      40.9   1.4   15000                                 2     13.4 Oleylamine                                                                            H.sub.3 PO.sub.4                                                                      25.2   1.1   20000                                 3     14.6 Butylamine                                                                            H.sub.3 PO.sub.4                                                                      38.1   0.2   20000                                 4     39.8 Tridecylamine                                                                         H.sub.2 SO.sub.4                                                                      43.4   --     4000                                                    (20.4 g)                                                   ______________________________________                                    

The detergent formulations described in Table 2 were produced usingcobuilder 1. Compositions A-M are compact detergents, N and O areexamples of color detergents and formulation P is a structured liquiddetergent. The abbreviations in Table 2 have the following meanings:

TAED: Tetraacetylethylenediamine

Soil release additive 1: Polyethylene terephthalate/polyoxyethyleneterephthalate in the molar ratio 3:2, molecular weight of a polyethyleneglycol in the condensate 4000, molecular weight of the polyester 10000

Soil release additive 2: Graft copolymer of vinyl acetate onpolyethylene glycol of molecular weight 8000, molecular weight of thegraft copolymer 24000

EO: Ethylene oxide

                                      TABLE 2                                     __________________________________________________________________________    Detergent compositions A-P                                                    Ingredients                                                                             A  B  C   D  E  F   G  H  I   J  K  L   M  N  O   P                 __________________________________________________________________________    Lin. alkyl-     6   6  1  8   9  7.5                 2.5    7.5               benzenesulfonate                                                              C.sub.12 -C.sub.18 -Alkyl                                                               9  9  2   3  12        1.5                                                                              10  9  9  9   9  5  9   2                 sulfate                                                                       C.sub.12 -Fatty alcohol ×     3                   2                     2 EO sulfate                                                                  C.sub.12 -C.sub.18 -Fatty        3  4.5       4   4                           alcohol × 4 EO                                                          C.sub.12 -C.sub.18 -Fatty                                                               10 10                                      13.5   4                 alcohol × 7 EO                                                          C.sub.13 -C.sub.15 -Oxo                                                                       7      5  8   10        10 10                                 alcohol × 7 EO                                                          C.sub.13 -C.sub.15 -Oxo                                                                           4.5          3                   2  7                     alcohol × 11 EO                                                         C.sub.16 -C.sub.18 -Glucamide       4                                         C.sub.12 -C.sub.14 -Alkyl                     4                               polyglucoside                                                                 C.sub.8 -C.sub.18 -Fatty acid                     6                           methyl-                                                                       tetraglycolamide                                                              Soap      2  2  1      0.5                                                                              2   0.5                                                                              0.6                                                                              1   2  2  2   2  1.5                                                                              2                     Na metasilicate ×                                                                 2  2  3.5       3             2  2  2   2                           5.5 H.sub.2 O                                                                 Na silicate         8         2.5                                                                              4                   0.5                      Mg silicate            0.8                        0.5                         Zeolite A 18 24 36  35 15 30  36.5                                                                             25 20  36 24 36  36    55  25                Zeolite P 18                                         36                       Sheet silicate                                                                             12        14           12                                        SKS 6 (Hoechst AG)                                                            Amorphous sodium                        12 12                                 disilicate                                                                    Sodium carbonate                                                                        12 12 12  11    15  10.5                                                                             10 8      12 12  12    6                     Sodium                 9                             6.5                      bicarbonate                                                                   Sodium citrate         5         7  4                       4                 TAED      4  4  3.5 3.5                                                                              5.5                                                                              3   4  3.8                                                                              5   4  4  4   4                           Perborate 4-H.sub.2 O                                                                         15  20    20     24                                           Perborate 2-H.sub.2 O         14.5                                            Percarbonate                                                                            15 15        18           20  15 15 15  15                          Carboxymethyl-                                                                          1  1  1.5 2.5                                                                              0.5                                                                              2   1  1.3                                                                              1.5 1  1  1   1  1  1                     cellulose                                                                     Soil release                                                                            0.8                                                                              0.8                                                                              0.8    0.5       0.5                                                                              0.5       0.5 0.5                                                                              0.5                      additive 1                                                                    Soil release                                  0.5 0.5                         additive 2                                                                    Lipase                 0.2                                                                              0.5    0.5                                                                              0.5       0.5 0.5       0.5               Protease               0.5                                                                              0.5    0.5                                                                              0.5       0.5 0.5   1   0.5               Cellulase              0.3                    0.2           0.2               Sodium sulfate                                                                          3  3  3   1.5                                                                              3.5                                                                              3   3.5                                                                              2.4    3  3  2.4 1.3                                                                              2                        Ethanol                                                                       Cobuilder 1                                                                             5  5  5   5  5  5   8  5  5   5  5  5   5  5  5   15                Phosphonate                         0.2           0.2       0.5               Opt. brightener                                                                         0.2                                                                              0.2                                                                              0.2    0.2       0.2                                                                              0.2       0.2 0.2       0.2               Color transfer                                       1.5                                                                              1                     inhibitor                                                                     Water           3.5    3.5          0.3 1  1  1      22.5                                                                             11  40.6              __________________________________________________________________________

Cobuilders 1 and 2 described in Table 1 are modified polyaspartic acidsto be used according to the invention, while cobuilders 3 and 4 lieoutside the invention.

In order to obtain further comparison with the prior art, polyasparticacids A, B and C were prepared in a known manner and tested ascobuilders in detergent formulations C, D and F shown in Table 2.

Preparation of Polyaspartic Acid A

Aspartic acid was condensed in the presence of phosphoric acid in themolar ratio 2:5 at 160° C. over the course of 6 hours as described inExample 5 of WO-A 95/16020. The polyaspartic acid had a residualphosphorus content of 0.9% and a molecular weight of 30000.

Polyaspartic Acid B

Prepared by condensing maleic anhydride with ammonia by the process ofDE-A 4 300 020. Molecular weight of the polyaspartic acid 3000.

Polyaspartic Acid C

Prepared by thermal condensation of L-aspartic acid at 210° C.,molecular weight of the polyaspartic acid 6000.

Further detergent formulations were produced by modifying detergentformulations C, D, F and I described in Table 2 by replacing cobuilder 1by the cobuilders described in Table 3 or preparing formulations which,for comparison, contained no cobuilder. The compositions of thesedetergent formulations are indicated in Table 2. Table 3 contains theresults obtained on testing the incrustation-inhibiting effect. Thedetergent formulations described in the table were in each case used towash test fabric made of cotton. The number of wash cycles was 15. Afterthis number of washes, the test fabric was ashed in each case in orderto determine the ash content of the fabric.

Washing conditions

Machine: Launder-o-meter from Atlas, Chicago

Number of wash cycles: 15

Wash liquor: 250 ml of liquor

Washing time: 30 min at 60° C.

Detergent dosage: 4.5 g/l

Water hardness: 22.40 German hardness (4 mmol/l Ca; Ca:Mg=4:1)

Test fabric: 20 g of cotton cheesecloth

                  TABLE 3                                                         ______________________________________                                        Incrustation inhibition by various cobuilders                                                                  Cobuilder                                                             Detergent                                                                             content in                                         Compar-            formulation                                                                           detergent                                    Ex-   ative              shown in                                                                              formulation                                                                           Ash                                  ample example  Cobuilder Table 2 [%]     [%]                                  ______________________________________                                        1     --       1         C       5       1.15                                 2     --       2         C       5       1.78                                 --    1        3         C       5       2.25                                 --    2        4         C       5       2.54                                 --    3        none      C       0       4.77                                 --    4        Polyaspartic                                                                            C       5       3.43                                                acid A                                                         --    5        Polyaspartic                                                                            C       5       4.46                                                acid B                                                         --    6        Polyaspartic                                                                            C       5       3.24                                                acid C                                                         3     --       1         J       5       2.49                                 4     --       2         J       5       2.07                                 --    7        none      J       0       4.2                                  5     --       2         D       5       1.89                                 --    8        Polyaspartic                                                                            D       5       2.85                                                acid A                                                         --    9        none      D       0       5.14                                 6     --       2         F       5       1.6                                  --    10       Polyaspartic                                                                            F       5       2.95                                                acid A                                                         --    11       Polyaspartic                                                                            F       5       4.38                                                acid B                                                         --    12       none      F       0       4.35                                 ______________________________________                                    

We claim:
 1. A detergent comprising at least one surfactant and anorganic cobuilder and, optionally, other conventional ingredients,wherein the organic cobuilder comprises 0.1 to 20% by weight of amodified polyaspartic acid obtained by polycondensation of aspartic acidin the presence of, in each case based on the aspartic acid employed,(a)2.5 to 25 mol % of amines having at least 8 carbon atoms, and (b) atleast 2% by weight of phosphoric acid, phosphorous acid, hypophosphorousacid, polyphosphoric acids, phosphorus pentoxide, phosphonic acids ormixtures of said acids,at temperatures of at least 120° C. andsubsequent hydrolysis with bases to produce the modified polyasparticacid having a phosphorus content of from 0.5 to 10% by weight.
 2. Adetergent as claimed in claim 1, wherein(a) primary and/or secondary C₈-C₂₂ -alkylamines, and (b) phosphoric acid, phosphorous acid,polyphosphoric acid or mixtures thereof, are employed in the preparationof the modified polyaspartic acid.
 3. A detergent as claimed in claim 1,wherein(a) dodecylamine, tridecylamine, cetylamine, stearylamine,palmitylamine, oleylamine, tallow fatty amine, coconut fatty amine,hydrogenated tallow fatty amine or mixtures of these amines, and (b)phosphoric acid and/or phosphorous acid, are employed in the preparationof the modified polyaspartic acid.
 4. A detergent as claimed in claim 1,wherein the phosphorus content of the modified polyaspartic acid is 0.6to 5% by weight.